TW201605972A - Flame-retardant polyurethane resin composition - Google Patents

Abstract

This flame-retardant urethane resin composition contains a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent and a foam stabilizer. With respect to a cured product of this flame-retardant urethane resin composition, the ratio of the peak intensity of a carbonyl group of isocyanurate to the peak intensity of a carbonyl group of urethane is within the range of from 0.3 to 3.5 as determined by means of 13C NMR.

Description

Flame retardant amine ester resin composition

The present invention relates to a flame retardant amine ester resin composition.

Concrete, which is reinforced by steel bars or the like, is used as a structural material for improving the strength of buildings, such as apartments, single-family houses, school facilities, and commercial buildings.

On the other hand, since concrete has heat storage property and cold storage property, there is a disadvantage that the interior of the summer building is heated by the accumulated heat, or the concrete is cooled during the cold winter, and the interior of the building is cooled. In order to reduce the influence of such external temperature on the interior of the building through concrete for a long time, the concrete is usually insulated.

Therefore, a rigid polyurethane foam having a flame retardancy for fire is used as the heat insulating layer.

Patent Document 1 describes a polyol composition for a rigid polyurethane foaming material comprising a polyol compound, a water-soluble organic solvent, a catalyst, a flame retardant, a foaming agent, and a polyisocyanate compound. It is described that the rigid polyurethane foam material obtained by mixing and foaming these components is excellent in flame retardancy.

Patent Document 2 describes 100 parts by weight of a polyol compound and a phosphate ester system. 10-30 parts by weight of a flame retardant, a foaming agent, a foam stabilizer, and a polyol composition for a polyurethane foaming material for a catalyst.

Patent Document 3 describes a flame-retardant rigid polyurethane foam obtained by reacting and curing a polyhydroxy compound, a polyisocyanate, an amine ester-forming catalyst, a flame retardant, a foam stabilizer, and a foaming agent.

Patent Document 4 describes a catalyst composition for producing a rigid polyurethane foam material and/or an isocyanurate modified rigid polyurethane foam material comprising a quaternary ammonium salt and a heterocyclic tertiary amine compound.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-053267

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-338651

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-200027

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-7079

None of the above Patent Documents 1 to 4 discloses the relationship between the ratio of the carbonyl group derived from the amine ester to the carbonyl group derived from the isocyanate and the incombustibility of the flame retardant amine ester resin composition.

An object of the present invention is to provide a flame retardant amine ester resin composition which exhibits high flame retardancy and is excellent in handling.

The flame retardant amine ester resin composition of the present invention is as follows.

Item 1. A flame retardant amine ester resin composition comprising a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer and an additive, and the flame retardant amine ester resin is composed of The intensity ratio of the peak of the carbonyl group of the trimeric isocyanate to the peak of the carbonyl group of the amine ester as measured by ¹³ C NMR of the cured product is between 0.3 and 3.5.

Item 2. The flame-retardant amine ester resin composition according to Item 1, wherein the additive contains red phosphorus as an essential component, and contains, in addition to the red phosphorus, a phosphate-containing, phosphate-containing flame retardant, and bromine-containing At least one of a flame retardant, a flame retardant containing cerium, and a metal hydroxide.

The flame-retardant amine ester resin composition according to Item 1 or 2, wherein the additive is 4.5 parts by weight to 70% based on 100 parts by weight of the amine ester resin composed of the polyisocyanate compound and the polyol compound. The range of parts by weight.

The flame-retardant amine ester resin composition according to any one of items 1 to 3, wherein the trimerization catalyst is 100 parts by weight of the amine ester resin composed of the polyisocyanate compound and the polyol compound. The standard is in the range of 0.1 to 10 parts by weight.

The flame-retardant amine ester resin composition according to any one of the items 1 to 4, wherein the foaming agent is based on 100 parts by weight of the amine ester resin composed of the polyisocyanate compound and the polyol compound. It is in the range of 0.1 to 30 parts by weight.

The flame retardant amine ester resin composition according to any one of items 1 to 5, wherein the aminoester resin has an isocyanate index of from 125 to 1,000.

Item 7. A combination for forming a flame retardant amine ester resin composition comprising (A) a first liquid containing a polyisocyanate compound, (B) a second liquid containing a polyol compound, and (C) trimerization Catalyst, (D) foaming agent, (E) foam stabilizer and (F) additive, and the carbonyl group of the trimer isocyanate as measured by ¹³ C NMR of the hardened amine ester resin composition The intensity ratio of the peak to the peak of the carbonyl group of the amine ester is between 0.3 and 3.5.

According to the present invention, there is provided a flame retardant amine ester resin composition which exhibits high flame retardancy and is excellent in handling.

Fig. 1 is a graph showing the results of solid-state NMR measurement of the flame-retardant amine ester resin compositions of Examples 1-3 and Comparative Example 1.

Fig. 2 is a graph showing the results of solid-state NMR measurement of the flame-retardant amine ester resin compositions of Examples 1 and 4.

The flame retardant amine ester resin composition of the present invention will be described.

First, an amine ester resin used for a flame retardant amine ester resin composition will be described.

The amine ester resin is composed of a polyisocyanate compound as a main component and a polyol compound as a curing agent.

Examples of the polyisocyanate compound include an aromatic polyisocyanate, an alicyclic polyisocyanate, and an aliphatic polyisocyanate.

Examples of the aromatic polyisocyanate include phenyl diisocyanate, methylphenyl diisocyanate, benzodimethyl diisocyanate, diphenylmethane diisocyanate, dimethyl diphenylmethane diisocyanate, triphenylmethane triisocyanate, and naphthalene. Diisocyanate, polymethylene polyphenyl Polyisocyanate, etc.

Examples of the alicyclic polyisocyanate include cyclohexyl diisocyanate, methylcyclohexyl diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyl dicyclohexylmethane diisocyanate, and the like.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethyl diisocyanate, propyl diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

One type or two or more types of polyisocyanate compounds can be used. The main component of the amine ester resin is preferably diphenylmethane diisocyanate for reasons of ease of use, availability, and the like.

Examples of the polyol compound as the curing agent of the amine ester resin include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols. Polymer polyol, polyether polyol, and the like.

Examples of the polylactone polyol include polypropane lactone diol, polycaprolactone diol, and polyvalerolactone diol.

Examples of the polycarbonate polyol include hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and decanediol, and ethylenedicarbonate and carbonic acid. A polyol obtained by a dealcoholization reaction such as propylene glycol or the like.

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolak.

Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.

Examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, and butylene glycol. Pentylene glycol, hexanediol, and the like.

Examples of the polyester polyol include a polymer obtained by dehydrating and condensing a polybasic acid with a polyhydric alcohol, and a polymerization obtained by ring-opening polymerization of a lactone such as ε-caprolactone or α-methyl-ε-caprolactone. And a condensate of the hydroxycarboxylic acid and the above polyol.

Here, specific examples of the polybasic acid include adipic acid, sebacic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Further, specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, and neopentyl Glycol and the like.

Further, specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

Examples of the polymer polyol include graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate or methacrylate onto an aromatic polyhydric alcohol, an alicyclic polyhydric alcohol, or an aliphatic polyhydric alcohol. A polymer obtained from a polyester polyol or the like, a polybutadiene polyol, a modified polyol of a polyhydric alcohol, or a hydride of the above.

Examples of the modified polyol of the polyhydric alcohol include those obtained by reacting an alkylene oxide with a polyol of a raw material.

Examples of the polyhydric alcohol include triols such as glycerin and trimethylolpropane; neopentyl alcohol, sorbitol, mannitol, sorbitol, diglycerin, and dipentaerythritol, and sucrose, glucose, and nectar. Four to eight-membered alcohols such as sugar, fructose, methyl glucoside and its derivatives; phenol, phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, indophenol, 1,4,5,8-tetrahydroxyindole, 1-hydroxyindole, etc.; polybutadiene Alcohol; castor oil polyol; (co)polymer of hydroxyalkyl (meth) acrylate and poly A polyfunctional (e.g., a functional group of 2 to 100) polyhydric alcohol such as vinyl alcohol or a condensate of phenol and formaldehyde (novolac).

The method of modifying the polyol is not particularly limited, and a method of adding alkylene oxide (hereinafter abbreviated as AO) can be preferably used.

Examples of the AO include AO having a carbon number of 2 to 6, and examples thereof include ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), and 1,3-propylene oxide. 1,2-butylene oxide, 1,4-butylene oxide, and the like.

Among these, from the viewpoint of properties or reactivity, PO, EO and 1,2-butylene oxide are preferable, and PO and EO are more preferable. As a method of adding two or more types of AO (for example, PO and EO), block addition may be employed, and random addition may be employed, and these may be used in combination.

The polyether polyol is, for example, at least one of an alkylene oxide such as ethylene oxide, propylene oxide or tetrahydrofuran, in the presence of at least one of a low molecular weight active hydrogen compound having two or more active hydrogens. A polymer obtained by ring polymerization.

Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include glycols such as bisphenol A, ethylene glycol, propylene glycol, butanediol, and 1,6-hexanediol; glycerin and trimethylol Triols such as propane; amines such as ethylenediamine and butanediamine.

The polyol used in the present invention is preferably a polyester polyol or a polyether polyol in terms of a large effect of reducing the total heat release amount at the time of combustion.

Among them, a polyester polyol having a molecular weight of 200 to 800 is more preferably used, and a polyester polyol having a molecular weight of 300 to 500 is further preferably used.

Further, the isocyanate index is a percentage ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound, and the value exceeding 100 means isocyanide. The acid ester group is in excess of the hydroxyl group.

The range of the isocyanate index of the amine ester resin used in the present invention is preferably in the range of from 125 to 1,000, more preferably in the range of from 200 to 800, and still more preferably in the range of from 300 to 700. The isocyanate index (INDEX) was calculated by the following method.

INDEX = equivalent number of isocyanate ÷ (number of equivalents of polyol + number of equivalents of water) × 100

Here, the number of equivalents of isocyanate = the number of parts used for polyisocyanate × NCO content (%) × 100 / NCO molecular weight

The number of equivalents of the polyol = OHV × the number of parts used of the polyol ÷ the molecular weight of KOH, the OHV is the hydroxyl value of the polyol (mg KOH / g), The number of equivalents of water = the number of parts used in water x the number of OH groups in water / the molecular weight of water.

Further, in the above formula, the unit of the use number is the weight (g), the molecular weight of the NCO group is 42, and the NCO content is the ratio of the NCO group in the polyisocyanate compound by mass%, in order to facilitate the unit of the above formula. In terms of conversion, the molecular weight of KOH was 56,100, the molecular weight of water was 18, and the number of OH groups of water was 2.

Further, the flame retardant amine ester resin composition contains a catalyst, a foaming agent, and a foam stabilizer.

Examples of the catalyst include triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethyl. Triamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N-methyl, N'-dimethylaminoethylper A catalyst containing a nitrogen atom such as an imidazole compound obtained by substituting a cyanoethyl group for a secondary amine functional group in the imidazole ring.

The amount of the catalyst to be used for the flame retardant amine ester resin composition is preferably in the range of 0.1 part by weight to 10 parts by weight, more preferably 0.1% by weight based on 100 parts by weight of the amine ester resin. The range of parts to 8 parts by weight, more preferably from 0.1 part by weight to 6 parts by weight, is preferably in the range of from 0.1 part by weight to 3.0 parts by weight.

When it is 0.1 part by weight or more, an abnormality which hinders the formation of the amine ester bond is not caused, and when it is 10 parts by weight or less, an appropriate foaming speed can be maintained and it is easy to handle.

A preferred catalyst includes a trimerization catalyst which reacts an isocyanate group contained in a polyisocyanate compound which is a main component of a polyurethane resin, and performs trimerization to promote formation of a trimerization isocyanate ring.

In order to promote the formation of a trimeric isocyanate ring, for example, as a catalyst, tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tri ((2,4,6-tri)) Dialkylaminoalkyl)hexahydrosymmetric three a nitrogen-containing aromatic compound; an alkali metal carboxylate such as potassium acetate, potassium 2-ethylhexanoate or potassium octylate; a tertiary ammonium salt such as a trimethylammonium salt, a triethylammonium salt or a triphenylammonium salt; a quaternary ammonium salt such as a tetramethylammonium salt, a tetraethylammonium salt or a tetraphenylammonium salt.

The addition amount of the trimerization catalyst for the flame retardant amine ester resin composition is preferably in the range of 0.6 part by weight to 10 parts by weight, more preferably 0.1 part by weight, per 100 parts by weight of the amine ester resin. The range of 8 parts by weight, more preferably 0.1 parts by weight to 6 parts by weight, is preferably in the range of 0.1 part by weight to 3.0 parts by weight. When it is 0.1 part by weight or more, the abnormality of the trimerization of the isocyanate is not caused, and when it is 10 parts by weight or less, an appropriate foaming speed can be maintained and it is easy to handle.

Further, the foaming agent for the flame retardant amine ester resin composition promotes foaming of the amine ester resin.

Specific examples of the foaming agent include water; low boiling point such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane or cycloheptane. Hydrocarbon; chlorinated aliphatic hydrocarbon compound such as dichloroethane, chloropropane, isochloropropane, chlorobutane, isochlorobutane, chloropentane, isochloropentane, trichloromonofluoromethane, trichlorotrifluoroethane Fluorine compounds such as alkane, hydrofluorocarbon such as CHF ₃ , CH ₂ F ₂ , CH ₃ F; dichloromonofluoroethane (eg HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluorocarbon) Methane), HCFC142b (1-chloro-1,1-difluoroethane), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3 Hydrochlorofluorocarbon such as 3-trifluorobutane; an ether compound such as diisopropyl ether; or an organic physical foaming agent such as a mixture of such compounds; inorganic physics such as nitrogen, oxygen, argon or carbon dioxide gas Foaming agent, etc.

The range of the foaming agent is preferably in the range of 0.1 part by weight to 30 parts by weight based on 100 parts by weight of the amine ester resin. The foaming agent is preferably in the range of from 0.1 part by weight to 18 parts by weight, more preferably from 0.5 part by weight to 18 parts by weight, even more preferably from 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the amine ester resin. range.

When the range of the foaming agent is 0.1 part by weight or more, the formation of bubbles is promoted, and a good foam can be obtained. When the amount is 30 parts by weight or less, the vaporization force can be prevented from becoming high and the bubbles become coarse.

Examples of the foam stabilizer used for the flame retardant amine ester resin composition include polyoxyalkylene stabilizers such as polyoxyalkylene alkyl ethers, polyoxyxylene foam stabilizers such as organic polyoxyalkylene oxides, and the like. Surfactant and the like.

The amount of the foam stabilizer to be used in the curing of the amine ester resin by the chemical reaction is appropriately set depending on the amine ester resin to be hardened by the chemical reaction, and if an example is given, for example, 100 parts by weight relative to the amine ester resin. It is preferably in the range of 0.1 part by weight to 10 parts by weight.

One type or two or more types of the catalyst, the foaming agent, and the foam stabilizer may be used.

Next, the additives used in the present invention will be described.

In one embodiment, the additive comprises at least one selected from the group consisting of red phosphorus, phosphate, phosphate-containing flame retardant, bromine-containing flame retardant, barium-containing flame retardant, and metal hydroxide. . In another embodiment, the additive comprises red phosphorus and at least one selected from the group consisting of a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a cerium-containing flame retardant, and a metal hydroxide. One. In still another embodiment, the additive comprises at least one selected from the group consisting of a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a cerium-containing flame retardant, and a metal hydroxide. .

The additive preferably contains red phosphorus. As a preferable combination of the additive to be used, for example, any of the following (a) to (i) can be mentioned. The additive is more preferably a red phosphorus-containing and phosphate-containing flame retardant.

(a) Red phosphorus and phosphate

(b) Red phosphorus and phosphate-containing flame retardants

(c) Red phosphorus and bromine-containing flame retardants

(d) Red phosphorus and flame retardant containing bismuth

(e) Red phosphorus and metal hydroxides

(f) Red phosphorus, phosphate esters and phosphate-containing flame retardants

(g) red phosphorus, phosphate and bromine-containing flame retardant

(h) Red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant

(i) Red phosphorus, phosphate esters, phosphate-containing flame retardants and bromine-containing flame retardants

With respect to the amount of the additive used in the present invention, the total amount of the additives other than the amine ester resin is preferably in the range of 4.5 parts by weight to 70 parts by weight, based on 100 parts by weight of the amine ester resin. It is preferably in the range of 4.5 parts by weight to 40 parts by weight, more preferably 4.5 parts by weight to 30 parts by weight, most preferably in the range of 4.5 parts by weight to 20 parts by weight.

When the range of the additive is 4.5 parts by weight or more, it is possible to prevent the molded article composed of the flame-retardant amine ester resin composition from being broken by the dense residue formed by the heat of the fire, and it is not hindered in the case of 70 parts by weight or less. Foaming of a flame retardant amine ester resin composition.

The red phosphorus used in the present invention is not limited, and a commercially available product can be appropriately selected and used.

In the case where red phosphorus is contained as an additive, the amount of red phosphorus to be used in the flame-resistant amine ester resin composition of the present invention is preferably from 3.0 parts by weight to 18 parts by weight based on 100 parts by weight of the amine ester resin. .

When the range of red phosphorus is 3.0 parts by weight or more, the self-extinguishing property of the flame-retardant amine ester resin composition is maintained, and in the case of 18 parts by weight or less, the flame retardant amine ester resin composition is not inhibited. Foaming.

Further, the phosphate ester used in the present invention is not particularly limited, and a monophosphate, a condensed phosphate or the like is preferably used.

The monophosphate is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, and tris(butoxyethyl) phosphate. , triphenyl phosphate, tricresyl phosphate, tris(dimethylphenyl) phosphate, tris(isopropylphenyl) phosphate, tris(phenylphenyl) phosphate, trinaphthyl phosphate, cresyl phosphate Diphenyl ester, diphenyl phosphate diphenyl ester, diphenyl phosphate (2-ethylhexyl) ester, di(isopropylphenyl) phosphate phenyl ester, monoisodecyl phosphate, 2-acrylic acid phosphate Ethoxyethyl ester, 2-methylpropenyloxyethyl acid phosphate, diphenyl phosphate-2-propenyloxyethyl ester, diphenyl phosphate-2-methylpropenyloxyethyl ester, Melamine phosphate, di-melamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresol Phosphine oxide, diphenyl phosphinate, diethyl phenylphosphonate, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), phosphaphenanthrene, phosphoric acid (β-chloropropyl) ester and the like.

The condensed phosphate ester is not particularly limited, and examples thereof include a trialkyl polyphosphate, a resorcinol polyphenyl phosphate, and a resorcinol polyphosphoric acid (di-2,6-dimethylphenyl) ester (large A condensed phosphate ester such as a product produced by Yasei Chemical Co., Ltd., trade name PX-200), hydroquinone polyphosphoric acid (2,6-dimethylphenyl) ester, and the like.

Examples of the commercially available condensed phosphate ester include resorcinol polyphenyl phenyl phosphate (trade name: CR-733S), bisphenol A polyphosphate cresyl ester (trade name: CR-741), and aromatic condensed phosphate ester. Trade name: CR747), resorcinol polyphenylphosphate (manufactured by Adeka Co., Ltd., trade name: Adekastab PFR), bisphenol A polycresol cresyl ester (manufactured by Adeka Co., Ltd., trade name: FP-600, FP-700).

Among the above, in order to improve the viscosity reduction effect in the composition before hardening and to reduce the initial heat release effect, it is preferred to use a monophosphate, and more preferably use a tris(?-chloropropyl) phosphate. .

One or two or more kinds of phosphate esters can be used.

The amount of the phosphate ester added is preferably from 1.5 parts by weight to 52 parts by weight, more preferably from 1.5 parts by weight to 20 parts by weight, even more preferably from 2.0 parts by weight to 100 parts by weight of the amine ester resin. The range of 15 parts by weight is preferably in the range of 2.0 parts by weight to 10 parts by weight.

When the range of the phosphate ester is 1.5 parts by weight or more, the self-extinguishing property is maintained, and when it is 52 parts by weight or less, the foaming of the flame-retardant amine ester resin composition is not inhibited.

Further, the phosphate-containing flame retardant used in the present invention is a phosphate-containing one.

The phosphoric acid used for the phosphate-containing flame retardant is not particularly limited, and examples thereof include monophosphoric acid and pyrophosphorus. Various phosphoric acids such as acid, polyphosphoric acid, and combinations thereof.

Examples of the phosphate-containing flame retardant include phosphates composed of various phosphoric acids and salts of at least one metal or compound selected from the group consisting of metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. . Examples of the metal of Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.

Further, examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine. Wait.

Further, examples of the aromatic amine include pyridine and tri , melamine, ammonium, etc.

Further, the phosphate-containing flame retardant may be subjected to a known water resistance improving treatment such as treatment with a decane coupling agent or coating with a melamine resin, and a known foaming auxiliary such as melamine or neopentyl alcohol may be added.

Specific examples of the phosphate-containing flame retardant include monophosphate, pyrophosphate, and polyphosphate.

The monophosphate is not particularly limited, and examples thereof include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, and phosphorous acid. Sodium salt such as sodium or sodium hypophosphite, potassium salt such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite, monolithium phosphate, dilithium phosphate, and phosphoric acid Lithium salts such as lithium, lithium phosphite, lithium diphosphite, lithium hypophosphite, cesium salts such as cesium dihydrogen phosphate, cesium hydrogen phosphate, triterpene phosphate, bismuth subphosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, a magnesium salt such as magnesium triphosphate or magnesium hypophosphite; a calcium salt such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate or calcium hypophosphite; or a zinc salt such as zinc phosphate, zinc phosphite or zinc hypophosphite.

Further, the polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate and polyphosphate. , melamine polyphosphate, ammonium polyphosphate amide, aluminum polyphosphate, and the like.

Among these, in order to improve the self-extinguishing property of the phosphate-containing flame retardant, it is preferred to use a monophosphate, and it is more preferable to use ammonium dihydrogen phosphate.

The phosphate-containing flame retardant may be used alone or in combination of two or more.

The amount of the phosphate-containing flame retardant to be used in the present invention is preferably from 1.5 parts by weight to 52 parts by weight, more preferably from 1.5 parts by weight to 20 parts by weight, per 100 parts by weight of the amine ester resin. The range is more preferably in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.

When the range of the phosphate-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the flame-retardant amine ester resin composition is maintained, and in the case of 52 parts by weight or less, the flame retardancy is not hindered. Foaming of the urethane resin composition.

In addition, the bromine-containing flame retardant to be used in the present invention is not particularly limited as long as it is a compound containing bromine in its molecular structure, and examples thereof include an aromatic brominated compound.

Specific examples of the aromatic brominated compound include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclopentane, decabromodiphenyl ether, and octabromodiphenyl ether. a monomeric organic bromine compound such as hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethyl-bis(tetrabromophthalimide) or tetrabromobisphenol A; a brominated polycarbonate such as a polycarbonate oligomer produced by using phenol A as a raw material, a copolymer of a polycarbonate oligomer and bisphenol A; and a reaction of brominated bisphenol A and epichlorohydrin a diepoxide compound, a brominated epoxy compound such as a monoepoxy compound produced by a reaction of a brominated phenol with epichlorohydrin; a poly(benzyl bromide acrylate); a brominated polyphenylene ether; a brominated bisphenol A, condensate of cyanuric chloride and brominated phenol; brominated polystyrene such as brominated (polystyrene), poly(brominated styrene), crosslinked brominated polystyrene; crosslinked or non-crossed Brominated poly(A) Halogenated bromine compound polymer such as styrene).

From the viewpoint of controlling the amount of heat generation at the initial stage of combustion, brominated polystyrene, hexabromobenzene or the like is preferable, and hexabromobenzene is more preferable.

The bromine-containing flame retardant may be used alone or in combination of two or more.

The amount of the bromine-containing flame retardant to be used in the present invention is preferably from 1.5 parts by weight to 52 parts by weight, more preferably from 1.5 parts by weight to 20 parts by weight, per 100 parts by weight of the amine ester resin. Further, it is preferably in the range of 2.0 parts by weight to 15 parts by weight, more preferably in the range of 2.0 parts by weight to 10 parts by weight.

When the range of the bromine-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the flame-retardant amine ester resin composition is maintained, and when it is 52 parts by weight or less, the flame retardant amine is not inhibited. Foaming of the ester resin composition.

Moreover, examples of the flame retardant containing ruthenium used in the present invention include ruthenium oxide, decanoate, and pyroantimonate.

Examples of the cerium oxide include antimony trioxide, antimony pentoxide, and the like.

Examples of the citrate include sodium citrate, potassium citrate, and the like.

Examples of the pyroantimonate include sodium pyroantimonate, potassium pyroantimonate, and the like.

The ruthenium-containing flame retardant used in the present invention is preferably ruthenium oxide.

The flame retardant containing cerium may be used alone or in combination of two or more.

The amount of the flame retardant containing cerium is preferably in the range of 1.5 parts by weight to 52 parts by weight, more preferably in the range of 1.5 parts by weight to 20 parts by weight, even more preferably 100 parts by weight of the amine ester resin. The range of from 2.0 parts by weight to 15 parts by weight is preferably in the range of from 2.0 parts by weight to 10 parts by weight.

When the range of the flame retardant containing cerium is 1.5 parts by weight or more, the self-extinguishing property of the flame-retardant amine ester resin composition is maintained, and when it is 52 parts by weight or less, the flame retardant amine is not hindered. Foaming of the ester resin composition.

Further, examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, and hydrogen. Copper oxide, vanadium hydroxide, tin hydroxide, and the like.

One type or two or more types of metal hydroxides can be used.

The amount of the metal hydroxide added is preferably in the range of 1.5 parts by weight to 52 parts by weight, more preferably in the range of 1.5 parts by weight to 20 parts by weight, even more preferably 2.0 parts by weight based on 100 parts by weight of the amine ester resin. The range of parts to 15 parts by weight is preferably in the range of from 2.0 parts by weight to 10 parts by weight.

When the range of the metal hydroxide is 1.5 parts by weight or more, the self-extinguishing property of the flame-retardant amine ester resin composition is maintained, and when it is 52 parts by weight or less, the flame retardant amine ester is not inhibited. Foaming of the resin composition.

Further, the flame retardant amine ester resin composition may be used in combination with an inorganic filler.

The inorganic filler is not particularly limited, and examples thereof include cerium oxide, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, cerium oxide, ferrite, and alkali. Magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, aluminum magnesium carbonate, calcium sulfate, barium sulfate, gypsum fiber, calcium citrate and the like, talc, clay, mica, montmorillonite, Bentonite, activated clay, sepiolite, filamentous aluminite, sericite, glass fiber, glass beads, alumina hollow spheres, aluminum nitride, boron nitride, tantalum nitride, carbon black, graphite, carbon fiber, carbon hollow Ball, carbon powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum Plate, molybdenum sulfide, tantalum carbide, stainless steel fiber, various magnetic powder, slag fiber, fly ash, cerium oxide alumina fiber, alumina fiber, cerium oxide fiber, zirconia fiber, and the like.

One or two or more kinds of inorganic fillers may be used.

Further, the flame-retardant amine ester resin composition may contain an antioxidant, a heat stabilizer, a metal damage inhibitor, an antistatic agent, such as a phenolic, amine, or sulfur system, as needed, without departing from the object of the present invention. An auxiliary component such as a stabilizer, a crosslinking agent, a lubricant, a softener, a pigment, an adhesion-imparting resin, or an adhesion-imparting agent such as polybutene or a petroleum resin.

Since the flame retardant amine ester resin composition is hardened by the reaction, its viscosity changes with the passage of time. Therefore, the flame retardant amine ester resin composition is divided into two or more parts before the use of the flame retardant amine ester resin composition, and the flame retardant amine ester resin composition is prevented from reacting and hardening. Further, when a flame retardant amine ester resin composition is used, a flame retardant amine ester resin composition can be obtained by integrating two or more flame retardant amine ester resin compositions into one portion.

In addition, when the flame retardant amine ester resin composition is divided into two or more parts, the flame retardant amine ester resin is not separately cured as long as the components of the flame retardant amine ester resin composition are divided into two or more parts. The components may be divided so that the components of the composition are mixed and the curing reaction is started.

The present invention also includes a system for forming a flame retardant amine ester resin composition for forming a first liquid comprising (A) a polyisocyanate-containing compound, (B) a second liquid containing a polyol compound, C) a combination or reaction system of a trimerization catalyst, (D) a foaming agent, (E) a foam stabilizer, and (F) an additive of a flame-retardant amine ester resin composition, which comprises a polyisocyanate compound, a polyol compound, A hardened substance of a flame retardant amine ester resin composition formed by mixing a trimerization catalyst, a foaming agent, a foam stabilizer and an additive, and a peak of a carbonyl group of a trimeric isocyanate as measured by ¹³ C NMR with respect to an amine ester The intensity ratio of the peak of the carbonyl group is between 0.3 and 3.5.

(C) a trimerization catalyst, (D) a foaming agent, (E) a foam stabilizer, and (F) an additive may be contained in the first liquid or the second liquid, respectively, and may also be combined with the first liquid and the second liquid Provided separately. Preferably, the (C) trimerization catalyst, the (D) foaming agent, the (E) foam stabilizer and the (F) additive are each contained in the second liquid. The system for forming the flame-retardant amine ester resin composition is provided in the form of a device including a first container for accommodating the first liquid and a second container for accommodating the second liquid, for example, a caulking gun or a spray container.

The details of the components (A) to (F) and the flame-retardant amine ester resin composition thus formed are as described above.

The flame-retardant amine ester resin composition of the present invention is characterized in that the peak of the carbonyl group of the trimeric isocyanate (A) relative to the carbonyl group of the amine ester when the hardened amine ester resin composition after hardening is measured by solid ¹³ C NMR The intensity ratio (A/B) of the peak (B) is between 0.3 and 3.5.

When the ratio is less than 0.3, the flame retardant amine ester resin composition is soft, flammable, and poor in shape retention. When the ratio exceeds 3.5, the strength of the foamed material becomes hard, and it tends to be brittle. According to the present invention, the quantification of the trimeric isocyanate ratio of the flame retardant amine ester resin composition by solid ¹³ C NMR is first achieved, and the flame retardant amine ester resin composition can be expressed in the above ratio of 0.3 to 3.5. It has high flame retardancy and excellent shape retention, so it is also excellent in handling.

In one embodiment, the flame retardant amine ester resin composition contains a trimerization catalyst in a range of 0.1 to 10 parts by weight based on 100 parts by weight of the amine ester resin composed of the polyisocyanate compound and the polyol compound. 0.1 to 30 parts by weight of a foaming agent, 0.1 part by weight to 10 parts by weight of a foam stabilizer, and 4.5 parts by weight to 70 parts by weight of an additive, a carbonyl group of a trimeric isocyanate as measured by ¹³ C NMR The intensity ratio of the peak to the peak of the carbonyl group of the amine ester is between 0.3 and 3.5.

The measurement method of solid ¹³ C NMR was carried out as follows: An 8 mm MAS probe was attached to an ECX400 NMR apparatus manufactured by JEOL RESONANCE Co., Ltd. The measurement system was measured using a single pulse method (DD/MAS method) with a 90° pulse of 6.6 μs and a magic angle rotation of 7.0 kHz. In the calculation of the chemical shift, the methyl group of hexamethylbenzene was used as an external standard (17.3 ppm). The probe to be used is not particularly limited and is selected depending on the capacity or outer diameter of the test tube. The delay time of the pulse irradiation is based on the T1 relaxation time of the ¹³ C nucleus of each peak obtained by the saturation recovery method or the like in advance so that the value at which the peak angle of each peak component is 90° becomes 5 times the peak of the longest T1. Mode setting.

The cumulative number of times varies depending on each sample, and is preferably performed at least once or more, preferably 64 times or more, and more preferably 640 times or more in order to obtain sufficient S/N for analysis.

A spectral broadening of 20 Hz was applied to the map, and thereafter, the peak intensity ratio of each peak was calculated from the NMR spectrum obtained by performing Fourier transform.

The peak intensity is set from the baseline to the height of the peak.

The method for producing the flame-retardant amine ester resin composition is not particularly limited. For example, a flame-retardant amine ester resin composition can be obtained by mixing the components of the flame-retardant amine ester resin composition; a method in which a flammable amine ester resin composition is suspended in an organic solvent or heated to be melted to form a coating; a method of dispersing in a solvent to prepare a slurry; and a composition comprising a flame retardant amine ester resin composition When the reaction-curable resin component contains a component which is solid at a temperature of 25 ° C, the flame-retardant amine ester resin composition is melted by heating or the like.

The flame retardant amine ester resin composition can be extruded by using a single screw extruder A well-known device such as a machine, a Bamburi mixer, a kneading mixer, a kneading roll, a kneading machine, or a planetary mixer is obtained by kneading each component of a flame-retardant amine ester resin composition.

Further, the main component of the amine ester resin and the curing agent may be separately kneaded together with a filler or the like in advance, and may be obtained by kneading with a static mixer or a dynamic mixer immediately before the injection.

Further, the components of the flame-retardant amine ester resin composition from which the catalyst is removed and the catalyst may be obtained by kneading in the same manner immediately before the injection. A flame retardant amine ester resin composition can be obtained by the method described above.

Next, a method of curing the flame-retardant amine ester resin composition of the present invention will be described.

When the components of the flame-retardant amine ester resin composition are mixed, the reaction starts, and the viscosity rises with the passage of time, and the fluidity is lost.

For example, the flame-retardant amine ester resin composition can be injected into a container such as a mold or a frame material to be cured, and a molded body composed of the flame-retardant amine ester resin composition can be obtained as a foam.

When a molded body composed of the above-mentioned flame retardant amine ester resin composition is obtained, it is possible to heat or apply pressure.

The molded body composed of the above-mentioned flame retardant amine ester resin composition is preferably in the range of 0.020 to 0.130, more preferably in the range of 0.030 to 0.100, and still more preferably 0.030 in terms of ease of handling. The range of 0.080 is preferably in the range of 0.040-0.060.

The peak of the carbonyl group of the trimeric isocyanate and the amine ester in the sample of the hardened flammable amine ester resin composition obtained by solid state ¹³ C NMR, that is, the cured product of the flame-retardant amine ester resin composition When the peak of the carbonyl group is measured, the surface layer of the upper surface of the hardened substance of the flame retardant amine ester resin composition is avoided, and the portion below the surface layer is measured. In the case of measuring a cured product of a flame-retardant amine ester resin composition applied to a wall surface or the like, it is preferred to take a sample from a portion which is 10% of the depth from the surface of the cured product.

Moreover, as a method of analyzing the trimerization catalyst contained in the sample of the cured flame-retardant amine ester resin composition, that is, the cured product of the flame-retardant amine ester resin composition, for example, a method can be mentioned. A method of extracting water having a water-soluble component of a hardened material by ion chromatography.

Next, an application example of the flame-retardant amine ester resin composition of the present invention will be described.

By spraying the flame-retardant amine ester resin composition onto a structure such as a building, a furniture, an automobile, a train, or a ship, a foam composed of a flame-retardant amine ester resin composition can be formed on the surface of the structure. Body layer.

For example, a method in which the flame-retardant amine ester resin composition is divided into a polyisocyanate compound and other components, and the two are sprayed and sprayed on the surface of the structure; A method in which a polyisocyanate compound is mixed with a component other than the component, and then sprayed onto the surface of the above structure. By the above method, a foam layer can be formed on the surface of the above structure.

Next, the fire resistance test performed on the fiber-reinforced resin molded article of the present invention will be described.

The molded article composed of the flame retardant amine ester resin composition was cut into a length of 10 cm, a width of 10 cm, and a thickness of 5 cm, and a sample for a tapered calorie test was prepared.

A sample of the tapered calorie test can be used, and the total amount of heat generated by the cone calorimeter test at a radiant heat intensity of 50 kW/m ^{2 for} 20 minutes is measured in accordance with the test method of ISO-5660.

Hereinafter, the present invention will be described more specifically by way of examples, but the invention is not limited thereto.

[Examples]

1. Manufacture of a flame retardant amine ester resin composition

According to the composition shown in Table 1, the flame-retardant amine ester resin compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were prepared. The details of each component in the table are as follows.

(1) Polyol composition

. Polyol compound

(A-1) terephthalic acid polyester polyol (manufactured by Kawasaki Chemical Industry Co., Ltd., product name: MAXIMOL RFK-505, hydroxyl value = 250 mgKOH/g)

. Foam stabilizer

Polyalkylene glycol foam stabilizer (manufactured by Dow Corning Toray, product name: SH-193)

. Trimerization catalyst

(A-1) Potassium 2-ethylhexanoate (manufactured by Tokyo Chemical Industry Co., Ltd., product code: P0048)

(A-2) Trimerization catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT-TR20)

(A-3) Trimerization catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT-TRX)

. Amine esterification catalyst

(B-1) pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT-DT)

(B-2) Amine esterification catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT-TT)

. Foaming agent

water

HFC HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Solvay, Japan) and HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by Central Glass Co., Ltd.), mixing ratio HFC-365mfc: HFC-245fa=7:3, hereinafter referred to as "HFC")

(2) Isocyanate compound (hereinafter referred to as "polyisocyanate")

MDI (manufactured by Japan Polyurethane Industry Co., Ltd., product name: MILLIONATE MR-200) Viscosity: 167mPa‧s

(3) Additives

(C-1) Red Phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: RINKA_FE 140)

(C-2) Ammonium dihydrogen phosphate (manufactured by Taiping Chemical Industry Co., Ltd.)

(C-3) Tris(β-chloropropyl) phosphate (manufactured by Daihatsu Chemical Co., Ltd., product name: TMCPP, hereinafter referred to as "TMCPP")

(C-4) Hexabromobenzene (manufactured by MANAC, product name: HBB-b, hereinafter referred to as "HBB")

(C-5) Aluminum hydroxide (manufactured by ALMORIX, product name: B-325)

(C-6) Antimony trioxide (manufactured by Nippon Concentrate Co., Ltd., product name: Patox C)

According to the composition of Table 1 below, the polyol compound, the foam stabilizer, various catalysts, the blowing agent for removing the HFC component, and the additive were weighed into a 1000 mL polypropylene beaker, and stirred at 25 ° C for 10 seconds using a hand mixer. . To the kneaded product after the stirring, a polyisocyanate compound and HFC were added, and the mixture was stirred by a hand mixer for about 10 seconds to prepare a foam. The obtained flame-retardant amine ester resin composition lost fluidity with the passage of time, and foams of the hardened flame-retardant amine ester resin compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were obtained.

2. Evaluation of foam

The foam was evaluated according to the following criteria, and the results are shown in Table 1 (the ratio of each component is expressed by weight based on 100 parts by weight of the polytrimeric isocyanate resin).

[Measurement of heat]

The self-hardened material was cut into a sample for a tapered calorie test in a manner of 10 cm × 10 cm × 5 cm, and the maximum heat release rate and total heat release amount when heated at a radiant heat intensity of 50 kW/m ^{2 for} 20 minutes were measured according to ISO-5660. The results are shown in Table 1.

This measurement method is the test of the test method according to ISO-5660 prescribed by the Buildings Comprehensive Test Institute as a public authority as defined by the Building Standards Act, in accordance with the test method of ISO-5660. law.

The total calorific value of the tapered calorie under heating for 10 minutes was 8 MJ/m ² or less and the condition of 9 MJ/m ² or less under heating for 20 minutes was acceptable. In this test, when it exceeds 8 MJ/m ² under heating for 10 minutes, it is ×, and when it is 10 minutes, it is 8 MJ/m ² or less, and when it is heated for 20 minutes, it exceeds 8 MJ/m ² and is 9 MJ/m ² or less. △, 10 minutes will 8MJ / m ² or less at 20 minutes and heated to a 8MJ / m ² or less as a person, will be at 10 minutes ○ 8MJ / m ² or less at 20 minutes and heated to a 6MJ / m ² or less is ◎.

[Measurement of expansion]

In the test of the above ISO-5660, the case where the expanded molded body was brought into contact with the igniter was taken as ×, and the case where it was not contacted was referred to as ○, and it is described in Table 1.

[Measurement of deformation (crack)]

When the test of the above-mentioned ISO-5660 is carried out, the case where the deformation of the back surface of the test sample is reached is regarded as ×, and the case where the deformation of the back surface is not observed is referred to as ○, and is described in Table 1-10.

[Measurement of shrinkage]

When the test of the above-mentioned ISO-5660 is carried out, a deformation of 1 cm or more in the lateral direction of the test sample and a deformation of 5 mm or more in the thickness direction can be seen as ×, and a case where no deformation is observed as ○ is described in Table 1.

[Comprehensive judgment]

The case where all of ○ or ◎ in the measurement of heat, expansion, deformation, and shrinkage was judged as OK, and the other was judged as NG.

3. Measurement by solid ¹³ C NMR

The samples of the cured products of the flame-retardant amine ester resin compositions of Examples 1 to 4 and Comparative Example 1 were subjected to ¹³ C NMR measurement. The measurement was carried out by mounting an 8 mm MAS probe on an ECX400 NMR apparatus manufactured by JEOL RESONANCE Co., Ltd., and the measurement was performed by a single pulse method (DD/MAS method) with a pulse of 6.6 μs at 90° and a rotation of 7.0 kHz at a magic angle. measuring. In the calculation of the chemical shift, the methyl group of hexamethylbenzene was used as an external standard (17.3 ppm). The delay time of the pulse irradiation is based on the T1 relaxation time of the ¹³ C nucleus of each peak obtained by the saturation recovery method or the like in such a manner that the value at which the peak angle of each peak component is 90° becomes the value of 5 times the longest peak of T1. set up. A spectral broadening of 20 Hz was applied to the map, and thereafter, the peak intensity ratio of each peak was calculated from the NMR spectrum obtained by performing Fourier transform. The peak intensity is set from the baseline to the height of the peak.

The measurement results are shown in Fig. 1 and Fig. 2. In Fig. 1, (a) is a peak derived from a carbonyl group of a trimeric isocyanate, (b) is a peak derived from a carbonyl group of an amine ester, (c) is a peak derived from an ester of a polyhydric alcohol, and (d) is derived from The peak of the aromatic ring, (e) is the peak derived from the ester. In Fig. 2, (a) is a peak derived from a carbonyl group of a trimeric isocyanate, and (b) is a peak derived from a carbonyl group of an amine ester. The intensity ratios of the peaks of the carbonyl groups of the trimeric isocyanate of the flame retardant amine ester resin compositions of Examples 1 to 4 to the peaks of the carbonyl groups of the amine esters were 1.16, 2.19, 3.08 and 2.29, respectively, and the flame retardant amine of Comparative Example 1 was used. The intensity ratio of the peak of the carbonyl group of the trimeric isocyanate of the ester resin composition to the peak of the carbonyl group of the amine ester was 0.20 (Table 2).

Claims (7)

A flame retardant urethane resin composition comprising a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer and an additive, and the flame retardancy The strength ratio of the carbonyl group of the isocyanurate to the peak of the carbonyl group of the amine ester when the cured product of the amine ester resin composition is measured by ¹³ C NMR is between 0.3 and 3.5. The flame retardant amine ester resin composition according to claim 1, wherein the additive contains red phosphorus as an essential component, and in addition to the red phosphorus, contains a phosphate-containing, phosphate-containing flame retardant, and bromine-containing At least one of a flame retardant, a flame retardant containing cerium, and a metal hydroxide. The flame retardant amine ester resin composition according to claim 1 or 2, wherein the additive is 4.5 parts by weight based on 100 parts by weight of the amine ester resin composed of the polyisocyanate compound and the polyol compound. A range of 70 parts by weight. The flame-retardant amine ester resin composition according to any one of claims 1 to 3, wherein the trimerization catalyst is 100 parts by weight of an amine ester resin composed of the polyisocyanate compound and the polyol compound. The standard is in the range of 0.1 to 10 parts by weight. The flame-retardant amine ester resin composition according to any one of claims 1 to 4, wherein the foaming agent is based on 100 parts by weight of the amine ester resin composed of the polyisocyanate compound and the polyol compound. It is in the range of 0.1 to 30 parts by weight. The flame retardant amine ester resin composition according to any one of claims 1 to 5, wherein the amino ester resin has an isocyanate index in the range of from 125 to 1,000. A combination for forming a flame retardant amine ester resin composition comprising (A) a first liquid containing a polyisocyanate compound, (B) a second liquid containing a polyol compound, and (C) a trimerization catalyst, (D) a foaming agent, (E) a foam stabilizer, and (F) an additive, a hardened substance of the flame retardant amine ester resin composition, a peak of a carbonyl group of a trimeric isocyanate as measured by ¹³ C NMR, relative to an amine ester The intensity ratio of the peak of the carbonyl group is between 0.3 and 3.5.